Process of preparing condensation products of the anthraquinone series



Patented Feb. 10, 1931- GEORG KRANZLEIN AND HEINRICH VQLLMANN} E-ERKKFoRT oN-TnE-Mhrtf HOCHST, GERMANY, ASSIGNORS T0 GENERAL ANILINE' WORKS} Il Tcif oF -i NEW? YORK, N. Y., A CORPORATION OF DELAWARE PROCESSOF PRERZr'RING GONDENSATION rRonUc'rs oEmi-I 'ANTHRAQUINoNE-sERIEs NoDrawing. Application filed July e, 1928, Serial No. 296,573, and'inGermany July 25, 1927 Our present invention relates to a new proc- .essof preparing; condensation products of the anthraquinone'series.

In U. S. patent specifications Nos. 1,564,584,

dated December '8, 1925', and 1,582,475 dated April 27, 1926, and in theco-pendingll S application of Georg KrttriZlein' and Robert "SedlmayrSer. No. 70,986 filed November 23,

"-ofox en.

- 1925, there are describedvat dyestuffs which can be obtained bycondensing benzanthrone with aromatic carboxylic-j acid chlorides orcarboxylic anhydrides'by means of aluminium chloride, advantageously inthe presence Now We have found that vat dyestuffs can likewise beobtained by condensing an arylketone of the following formula:

aryl 1 which contains hydrogen atoms in the 4-, 5-

and 8-positions, but maybe substituted in the remaining positions, bymeans of aluminium chloride or sodium-aluminium chloride in thebenzanthrone (cf.v Liebigs Annalen der Chemie volume 394;, page 143).The process according to this invention involves, however, aconsiderable technical advantage over the processes above referred to,since it'ren ders it possible to obtain the same favorableresult,by'substituting for the comparatively expensive benzanthrone acheaper naphtha.-

' lene derivative.

' The following examples are given by wa of illustration, it beingunderstood that they are in no way limitative; the parts are by weight:7 i r 1.' 46" parts of i a benioylnaphthalenei are mixed with ten timestheir weight ofjam'mia' ium chloride and 1'40 parts of benzoyl chlorideand molten at'about 125 C. for a prolonged time, say 20*to (SO-hours,with introduction of oxygen; 0n decomposing the melt with water, thecrudefdyestuff precipitates in the form of brown flakes. The crudeproduct is purified by treating it with a solution of sodiumhypochlorite containing; "10 to I 12 per cent 1 o'f re-active chlorineor by revat ting it,"and" thus 'yields the golden-yellow-3A849-dibenzpyrenquinoneali;1O of=t1re fol lowingformulaz f. r

parts of ibn ph h lene are 5 finely ground (triturated) with 230 partsof aluminium chloride andtliemixture'is stirred at about 120 C. to 130C. for about 2 to 3 hours. There are then' added another 230 partsofaluminium chloride and 140 parts of benzoyl c liloride and the melt isstirred at about 1259 C. 7 for about'48' hours,v xygen. be

worked up and purified in the manner in'di Cated'in theprecedingkexampleu dye- Stu?thusfobtainedfis"identical with the dyestuffobtained-according to Example 1.

3. 4O partsfof ia-benZoylnaphthaIen-e "are mixed, while stirring andintroducing airy withlOO parts ofsodium-aluminium chloride 9 at about C,tog- C. for 2 hours.

There are then gradually added 80 parts of 1 benzoyl chloride andthetemperature iskept 0., the introduction-of air being cone 'tinued.After about 48 hours the melt is de 95 composed and the crude productispurified in y theusual manner. Thedyestuff thus obtained is, identicalwithethat obtainable jac- 7 ez eifieemp 4. By meltinga-benzoylnaphthalene with r quinones which consists in reacting in theother positions, with aluminium chloride and benzoyl chloride. 7

4. The process for making dibenzpyrenquinones which consists in reactingin the presence of oxygen at a temperature of between 110 C. and 150C.upon zoylnaphthalene of the formula:

presence of oxygen at a temperature of between 110 C. and 150 C. upon anarylketone ofthc following formula:

' aryl eds 7 l I 2 6 5 -4 which contains,- hydrogen atoms in the 4-, 5-

and 8- positions, but may be substituted in the other positions, withaluminium chloride and a compound of the following formula: aryl-COX,wherein X stands for a halogen atom or for the group OCO-a-ryl.

2. The process for making dibenzpyrenquinones which consists in reactingin the presence of oxygen at a temperature of between 110 C. and 150 C.upon a-benzoylnaphthalene of the formula with aluminium chloride. V V V5. The process for making dibenzpyren- 1 a-benchloride and ben zoylquinones which consists in. reacting with alunnmum chloride and benzoylchloride in the presence of oxygen at about 125 C. for 20 to hours upona-benzoylnaphthalene of the formula tures.

with aluminium chloride and a compound of the following formula:aryl'CO' X, wherein X stands for a halogen atomforifor the group -OCOaryl. V r r 1 3. The process for making 'dibenzpyrenquinones whichconsists in reacting in the presence of oxygen at a temperature ofbetween 110C. and 150 C. upon anarylketone of the following formula: y 7V which contains hydrogen atoms in the 4-, 5-

- and 8-positions, but may be substituted in the In testimony whereof;we affix our signa- GEO'RG K ANZLEIN. HEIN IGH'VOLLMANN.

